Polyazo dyestuffs



Patented June 2, i 1953 UNITED STATES PATENT OFFICE POLYAZ O DYESTUFFSHans Ischer, Ernst Iselin, and Walter Wehrli, Basel, Switzerland,assignors to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing.Application February 4, 1952, Se-

rial N0. 269,897. 1951 9 Claims. 1 The present invention relates topolyazo dyestufis.

The new valuable polyazo dyestuffs provided by the present inventioncorrespond to the formula wherein:

the C-atom of the latter substitutent being connected with R,

w stands for a hydrogen atom when y denotes -OH, --OCH3 or --COOH, andstands for Cuwhen :1; denotes O- or being in complex linkage with y and--azo, n is a whole number and at least 1,

and wherein:

on I) or the copper complex thereof wherein the azo In SwitzerlandFebruary 14,

group is connectedto the 1- or fi-positioned carbon atom of thenaphthalene nucleus, and

R stands for the radical of a diazo component of the benzene serieshaving in ortho-position to the azo group a substituent capable of metalcomplex formation, or for the radical of a disazodiazo component of theformula OCH;

AN=N-BN= wherein A stands for the radical of a cliazo component of thebenzene or naphthalene series, B stands for a radical of the benzene ornaphthalene series, the adjacent azo groups being in pposition withrespect to each other,

and wherein the nucleus 0' may be further-substituted by methyl, methoxyor acylamino,

the coupling being efiected, in those cases where the radical R has thefirst-mentioned significance, with the .diazo component of anaminodisazo dyestuff of the formula OCH:

wherein A, B and C have the afore-indicatedsignificances, and in thosecases where R has the second-mentioned significance, with the diazocompound of an amine of the benzene series which carries inortho-position to the amino group a substituent capable of metal complexformation, and then treating the resulting polyazo dyestufi, whichshould contain at least two sulfonic acid groups, in substance or on thefiber with copper-yielding agents.

Illustrative of diazo components of the benzene series, which correspondto the first-mentioned significance of R, are inter alia the followingamines: 2-amino-1-methoxybenzene, 2-amin0-1 methoxy-4-methylbenzene,2-amino-1-methoxy 5-chlorobenzene, 2-amino-l-methoxybenzene-isulfonicacid, 2-amino-1-methoxy-5'-nitrobenzen'ei-sulfonic acid,2-amino-1-methoxy-5-chlorobenzene-e-sulfonic acid,2-amino-l-hydroxybenzenel-sulfonic acid,2-amino-1-hydroxybenthalene-5,7-disulfonic acid,

zene-4,6disulfonic acid, 2amino-1-hydroxy-6 chlorobenzene--sulionicacid, 2-a1nino-l-hydroxyi-chlorobenzene-6-sulfonic acid, 2-amino-1-hydroxy-5-nitrobenzene, 2-amino-l-hydroxy- 4-chloro-5-nitrobenzene,Z-amino-l-hydroxyinitrobenzene-S-sulfonic acid,2-amino-1-hydroxy-6-nitrobenzene-4-sulfonic acid,2-aminobenzene-l-carboxylic acid, 2-amino-5-nitrobenzene-l-carboxylicacid, zene-l-carboylic acid, boxy-d-sulfonic acid, boxy-S-sulfonic acid,etc.

The aminodisazo dyestuffs corresponding to the second-mentionedsignificance of R, may for instance be prepared by diazotizing astarting component A, for example l-aminobenzene-2,5- disulfonic acid,coupling the resultant diazo compound in weakly acid medium with amiddle component B, for example 3-amino-l-methylbenzene, furtherdiazotizing the thus-obtained monoazo dyestufi, and coupling thediazotized product with a component capable of metal complex formation,for example e-methyl-l-methoxy-Z-aminobenzene, in weakly acid medium.However, the aminodisazo dyestuffs corresponding to the aforesaiddefinition may-also 2-aminobenzene-l-car- 2-aminobenzene-l-carbeproduced by coupling, for example, the diazocompound of1-amino-4-nitrobenzene-2-sul fonic acid in alkaline medium with al-hydroxybenzene-2-carboxylic acid, reducing the nitro group of theresultant monoazo clyestufi by means of sodium sulfide, then furtherdiazotizingv and coupling the thus-diazotized product with a middlecomponent capable of metal complex formation, such for example asl-methoxy-2- amino-4-acetylaminobenzene, in weakly acid medium.

Illustrative of starting or initial components A for the preparation ofthe said aminodisazo dyestuffs are inter alia: aminobenzene, 1-amino-2-f methylbenzene, 1-amino-3-methylbenzene, 1- amino--methylbenzene,l-amino-2,3-dimethylbenzene, 1 amino 2,4 dimethylbenzene, 1- amino 2,5dimethylbenzene, 1-amino-2,6-dimethylbenzene, 1 aminobenzene 2 sulfonicacid, l-aminobenzene-3-sulfonic acid, 1- aminoboxylic acid,1-amino-3-hydroxybenzene-4-carboxylic acid,l-amino-3-methyl-4-hydroxybenzene-5-carboxylic acid,l-amino-l-hydroxybenzene' 5 carboxy 3 sulfonic acid, 1-amino-4-acetylaminobenzene-Z-sulfonic acid, as wellas other aminobenzenessubstituted by SO3H, -COOH, halogen, OII, alkoxy and/or alkyl groups;also l-aminonaphthalene, 2-aminonaphthalene,2-aminonaphthalene-3-carboxylic acid, l-aminonaphthalene-4-sulfonicacid, 1- aminonaphthalene-5-sulfonic acid, l-aminonaphthalene-S-sulfonicacid, l-aminonaphthalene-3,6-disulfonic acid, l-aminonaphthalene-4,8-disulfonic acid, 1-aminonaphthalene-3,8-disulfonic acid,Z-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-6sulfonic acid,2- aminonaphthalene 8 sulfonic acid, Z-aminonaphthalene-4,8-disulfonicacid, Z-aminonaph- 2-aminonaphthalene-6,8-disulfonic acid,2-aminonaphthalene-3,- fi-disulfonic acid, 1-aminonaphthalene-3,6,8e

trisulfonic acid, as well as other aminonaphthalene sulfonic acids.

Illustrative of middle components B are inter alia: aminobenzene,1-amino-3-methylbenzene, l-amino-2,5-dimethylbenzene,1-amino-2-methoxybenzene, l-amino-3-methoxybenzene,lamino-2-methyl-5-methoxybenzene, 1-amino- 2,5-dimethoxybenzene,1-amino-2,5-diethoxybenzene, 1 amino 3 acetylaminobenzene, 1- amino 2methoxy 5-acetylaminobenzene, iaminonaphthalene,1-aminonaphthalene6-sulfonic acid, 1-aminonaphthalene7-sulfonic acid,lamino 2 methoxynaphthalene, 1-amino-2- ethoxynaphthalene,1-amino-2-methylnaphthalene, 1-amino-2-methoxynaphthalene-6-sulfonicacid, 1-amino-2-ethoxynaphthalene-6-sulfonic acid, etc. Instead of amonoazo dyestuff from an initial component A and a middle component B,it is also possible to use for example -amino- 1,1 azobenzene, 4amino-1,1'-azobenZene-4- sulfonic acid or 4-amino-1,l-azobenzene-3,4-disulfonic acid.

Illustrative of amines of nucleus C are inter alia:1-amino-2-methoxybenzene, l-amino-2- methoxy 5 methylbenzene,l-amino-2,5-dimethoxybenzene, 1-amino-2-methoXy-5acetylaminobenzene, lamino-2-methoxy-5-formylaminobenzene,1-amino-2-methoxy-5-benzoylaminobenzene,l-amino-2-methoxy-5-cinnamoylaminobenzene, etc;

The azo dyestufis of composition (I), supra, which are derived from2,5dihydroxynaphtha lene and which serve as coupling components for thepreparation of the polyazo dyestuifs may be obtained for example fromthe corresponding 2-amino-5-hydroxynaphthalene-7-sulfonic acid dyestufisby replacement of the 2-positioned amino group by an hydroxyl group orby coupling onto 2,5-dihydroxynaphthalene-7-sulfonic acid. The combiningof thesedyestufis to the polyazo dyestuffs may, in many casesadvantageously be carried out with the copper complex compounds of thedyestufis and in the presence of an organic base such as pyridine,quinoline, etc. at temperatures of 0 to 60 C.

The afore-enumerated components are selected, according to theinvention, so that the final dyestuffs contain at least two s'ulfonicacid groups. By definition, moreover, these dyestufis also contain atleast two copperable azo bridges. However, additional groupings capableof copper complex formation may be present, as'for instance in the casewhere A is the radical of 2- hydroxybenzene-l-carboxylic acid.

The new polyazo dyestuffs, which dye cotton and regenerated cellulose ingray shades of good iastness to light and to washing, can beaftercoppered on the fiber, the resultant dyeings being of excellentfastness to light and washing. They may also be converted into thecopperficomplex compounds in substance, in which case the treatment withcopper-yielding agents is advantagecusly carried out in such manner thatthe methoxy groups are split. This may be effected according to variousmethods known from the literature, for example by heating with coppersalts in weakly acid to alkaline medium in the presence or absence ofammonia, organic bases, and optionally with the use of superatmosphericpressure, or-in a fusion of alkali salts of low molecular weightaliphatic carboxylic acids. The copper complex compounds dye cotton andregenerated cellulose in reddish to greenish gray shades of outstandingfastness to light and to washing.

The following examplesset forth representative exemplary embodiments ofthe invention, and these examples are intended to be solely illustrativeand not at all limitative. In these examples, the parts and percentagesare by weight 6 nobenzene-l-carboxylic acid to form the tetrakisazodyestufi, and then subjecting the latter to demethylating coppering inthe precedingly described manner.

and the temperatures are expressed in degrees {5 Dyestuffs with similarproperties are obtained centigrade. when, while otherwise proceeding asaforede- Example 1 scribed in the present example, the initial compo-52.9 parts of the aminodisazo dyestuflf, obtained correspondmg to (I)replaced by the by coupling diazotized Z-hydroxy-S-aminoben- 9eqtlvalent amount of y zene-l-carboxylic acid with l-aminonaphtha- 1ammobenzone'g'sulfomc lene-7-su1fonic acid, further diazotizing andcouboxy3ammobenzeneo'sumomc aold Dung with 2 amin0 1 methoXy 4 methy1bendroxy-1-carboxy-5-am1no-3-methylbenzene, 2- zene, are stirred into 500parts of water, '7 parts of hydroxy'l'oarboxy5'ammo 4 methylbonzone'sodium nitrite added, and the resultant massz'hydmxy'l'carboxy4'ammobenzene 2 then adjusted so that it is acid toCongo by the o' f' o oo addition of 50 parts of concentratedhydrochloric when Startmg Z any of the above mltlol acid at 10 12o andWhile stirring thoroughly. pcnents, the middle component correspondingto The diazotization will be completed in 2 to 3 is replaced by thecorresponding amount of hours. The obtained diazo suspension is then1-aminonaphthalene-fi-sulfonic aoid, added at room temperature to asolution of 45 methoxynaphthalono'6"s1fonio acid or parts f the coppercomplex of the monoazo e- 2-ethoxynaphthalene-6-sulfcnic acid, or when,stuff, obtained by the acid coupling of diazotized in any one of theaforementioned combinations, 2-aminobenzene-l-carboxylic acid withZ-aminothe second middle component c spondin to5-hydroxynaphthalene-7-sulfonic acid, followed 05 5 plg d by 1the cospondin am u O by replacement of the amino group by hydroxyl -mc oxy--am 11 8, -mB OXy-2amiand coppering, in 400 parts of water, 1000 partsno4-ac'etylaminobenzene, l-methoxy-Z-aminoof pyridine and parts ofconcentrated aqueous e-formylaminobenzene, 1-methoxy-2-amino-4- ammonia,whereby coupling to form the tetrabenzoylaminobenzene, 1 methoxy 2amino-4- kisazo dyestufi takes place instantaneously. Thetoluylaminobenzene, 1-methoxy-2-amino-4-cinmass is then adjusted to weakacidity with glanamoylaminobenzene or 1,4-dimethoxy-2-amicial aceticacid, filtered, and the thus-separated nobenzene, or when, in any of theprecedingly product stirred in 1000 parts of water, made a1kadescribedcombinations, the moiety (IV) is reline with sodium carbcfifnate and thedyestufi placed by the radical of 2-amino-1-carboxybensalted out andfiltered o zenel-sulfonic acid, Z-amino-l-c r The new dyestuff dyescotton and regenerated zene-5-sulfonic acid, 2-aminobenzirl -if dicellulose in y shades wh h, p n r r carboxylic acid,2-aminobenzene-1,4-dicarboxylic ment wi pp alts, becomes fast to lightand acid, 2 amino 5 chlorozenzene 1' carboxylic to washing. acid,2-amino-5-nitrobenzene-1-carbox 1i i For conversion thereof into thecopper complex 2-amino-1-methoxybenzene, 2-amino 1 m e tli in substance,the dyestufi is dissolved in 1500 oxybenzene4sulfonic acid,Z-amino-l-methoxyparts of water at 90, admixed with a solution ofbenzene 5 gulfonjc acid, 2 amino 5 agety]- 24.9 part f y lliz d coppersulfate in 100 aminobenzene-l-carboxylic acid, Z-amino-S- parts of waterand 25 parts of concentrated aquebenzoylaminobenzene-l-carboxylic acid,2-amim nia, and stirred for 6 to 10 hours at 90 no-l-h drox-5-nitrobenzene, 2-amino 1 33 QZg uZtiI the methoxy groups are split.The droxy 4 cli loro 5 nitrobenzene, 2 amino l resultant dyestuff, Whichcorresponds to the formethoxy-l-nitrobenzene, z-amino-l-hydroxyimulachlorobenzene-G-sulfonic acid, 2-amino-1-hy- COOH o qu0 HO- -N=N- N= N=NCH; Hots -oou-o-o= l 0311 N It (I) (I (IV) is salted out, filtered offand dried under reduced pressure at 90.

The identical dyestuff can be prepared by 'com-,

bining the diazo compound of the aminodisazo dyestufi in the presence ofsodium bicarbonate with 2,5-dihydroxy-naphthalene-7-sulfonic acid, thencoupling the resultant coupling product in the presence of pyridine withdiazotized Z-ami- COOH droXy l-nitmbenZene-B-sulfonic acid, 2-amino-1-hydroxy-6-nitrobenzene-4-sulfonic acid or 2- I t sou:

7 can for example also-be prepared, and this dyestuff yields dyeings ofvery similar-properties on cotton or regenerated cellulose.

Example 2 57.3 parts of the aminodisazo dyestuff, obtained by couplingdiazotized 2-hydroxy-1-carboxyaminobenZene-3-sulfonic acid withS-amino-lmethylbenzene, further diazotizing and couplin with2-amino-1-methoxy-4-methylbenzene, are diazotized in the mannerdescribed in Example 1 and then added at to to a solution of 53 parts ofthe copper complex of the monoazo dyestuif, obtained by the acidcoupling of diazotized 2- amino-l-carboxybenzenei-sulfonic followed byreplacement of the amino group by hydroxyl and coppering, in 250 partsof water,

800 parts of pyridine and parts of concentrated aqueous ammonia. Thecoupling to the tetrakisazo dyestufi takes place very quickly. Thereadily-soluble dyestuff is heated to 90 and is then coppered at 90-95by the addition of 25 parts of crystallized copper sulfate, dissolved in100 parts of water, until the methoxy group is split. The finisheddyestufi, which corresponds to the formula acid with 152-amino-5-hydroxynaphthalene-7-sulfonic acid,

thalene, or when, in any of the foregoing combinations, the componentscorresponding to (III) and (IV) are replaced by one of the components(III) and (IV) mentioned in Example 1.

Emctmple 3 56.7 parts of the disazo dyestuif, obtained by couplingdiazotized 2-aminonaphthalene-4,8-disulfonic acid with3-amino-1-methylbenzene,

10 further diazotizing and coupling with 2-aminolA-dimethoxybenzene, arediazotized as in Example 1, and the obtained diazo compound combined atroom temperature with the solution of 49.6 parts of the copper complexof the monoazo 'dyestufi, obtained by the acid coupling of diazotized2-amino-5-nitrobenzene-l-carboxylic acid with2-amino-5-hydroxynaphthalene-'l-sulfonic acid, followed by replacementof the amino group by hydroxyl and then conversion into the coppercomplex, in 600 parts of water and 1500 parts of pyridine. After heatingfor two more hours at -60, the coupling is completed. The obtaineddyestufi solution is then heated to 90 and, to efiect the coppering ofthe tetrakisazo dyestufi, 25 parts of crystallized copper sulfate,dissolved in 100 parts of water and 25 parts of concentrated aqueousammonia, are added and 00011 O-Cu0 I 1 03H 1 on; on: HO3S- -o-cu-oc=o lN C} 03H 1 r II) (III) is filtered off, after adjustment of the mass toweak acidity by means of glacial acetic acid, and is then stirred into1000 parts of water and converted into the sodium salt by the additionof sodium carbonate. The product is then salted. out, filtered off anddriedat 90 under reduced pressure.

The new dyestufi is a black powder and dyes S oan cotton and regeneratedcellulosein greenish gray shades of very good fastness to light and towashing. By aftertreatment on the fiber with copper salts, the wetfastnessproperties are further improved.

Dyestufiswith similar properties are obtained when while otherwiseproceeding as precedingly described in this example, the initialcomponent corresponding to (I) is replaced by an equivalent quantity of2 hydroxy 1 carboxy-3- aminobenzene-5-sulfonic acid, or when, startingfrom the aforesaid initial components, the middle componentcorresponding to (II) is replaced by the equivalent quantity ofaminobenzene, 2-

- amino 1 methoxybenzene, '2 amino 1,4 di- 7 methylbenzene,2-amino-lA-dimethoxybenzene, 2-amino-1,4-diethoxybenzene,3-amino-l-acetylaminobenzene, 2 -.amino '1 methoxyl-acetylaminobenzene,1-ami n onaphthalene, 1-amino-2- methoxynaphthalene orl-amino-Z-ethoxynaphthe mixture stirred for 8 to 10 hours at 90 to 95until formation of the copper complex, with splitting of the methoxygroup, is completed. The

dyestuff is then isolated after the manner described in Example 2 andconverted into the soggum salt, precipitated, filtered oh and dried atThe new dyestuff of the formula 0 Qu-O l l l -N=iii H, Hols -o-cu-o c=o1 N 1 I NO:

acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-

aminonaphthalene-3,6-disulfonic acid, l-aminonaphthalene-3,fi-disulfonicacid, l-aminonaphthalene 3,8 disulfonic acid, l-aminonaphthalene-4,8-..disulfonic acid, l-amino-naphthalene- 0 3,6,8-trisulfonic acid,l-amino-B-hydroxynaphthalene-3',6-disulfonic acid, 1-aminobenzene-2,4-disulfonic acid or 1-aminobenzene-2,5-disulfonic ac d, or when, startingfrom any one of the above in tial components, the first middle componentcorresponding to (II) is replaced by an equivalent 2,640,824 9 quantityof one. of the (II) compounds mention of the copper complex. Thedyestufi sotioned in Examples 1 and 2, or when, in any lution isthereupon acidified with glacial acetic of the preceding combinations,the components acid, the precipitated dyestufi is filtered OE andcorresponding to (HI) and (IV) are replaced by is then converted intothe sodium salt by preany of the components (III) and (IV) enumer- 5cipitation from soda-alkaline solution. The dyeated in Example 1. stufi,which corresponds to the formula Thus, in analogous manner, thedyestuffs 0f the is isolated and dried at 90 under reduced presfollowingformulae may be prepared: sure. It is a dark powder and dyes cotton andt i t Ho3s -N=NON=N-Q-N=N (2H5 H; HOaS- -o-ou o-o=o l 0311 N=N N0.

son; I o Ou0 l I i I Hogs H3 om H038 -oou-oo=o I N 1% N0:

Nnooom H058 Dyeings on cotton or regenerated cellulose, preregeneratedcellulose in gray shades of excellent pared with these dyestufis, arealso greenish gray fastnessto light and to washing. and very fast to lit and t0 W h ng. Dyestuffs with similar properties are obtained Example4 when, while otherwise proceeding as described in 50 this example, thecomponents corresponding to 13.? par s f 2-amin0benzene-lcarboxylic acid(I), (II), (III) and (IV) are severally replaced are dissolved in 200parts of Water and parts of hydrochloric acid of strength, and digigl zg components enumerated m azotized at 05 with 6.9 parts of sodiumnitrite.

The diazonium solution is combined at 10 with Example 5 the stronglysoda-alkaline (sodium carbonate) solution of 24 parts of2,5-dihydroxynaphtha- 92 parts of the trisazo dyestuff, o tai ed by lene'7 sulfonic acid. The monoazo dyestufi p g diazotizedl-aminonaphthalene-4-suL form nnmediately and, upon completion of tfonic acid with 1-aminonaphthalene-7-sulfonic coupling, is salted outand filtered on. The thus- 50 acid, further diazotizing and coupl Withobtained coupling component is dissolved in 300 1 methOXY 2 amino 4acetylaminobenzene parts of water, 750 parts of pyridine and 25 partsand then again dia-zotiz ing and qgupling t of concentrated aqueousammonia and is com- 2,5-di'hydroxyiiaDhthalene-Z-sulforiicacid in thebined at 40 with the diazonium solution, 010- 1 presence of sodiumbicarbonate, are dissolved in tained according to Example 1, from 52.7par-ts 35 600 parts of water, 1000 par-ts of pyridine n 5,

of the disazo dyestufi obtained by coupling diparts of concentratedaqueous ammonia. To the azotized 1-aminobenzene-2,5disulfonic acid withresultant solution, there is added dropwise at 20 l-aminonaphthalene,further diazotizing and an aqueous suspension of the diazo compoundcoupling with 2-amino-l-methoxy-4-methylbenfrom 20.3 parts of1-methoxy-2-aminob nz zene. After stirring for 5 hours, the coupling is4-sulfonic acid. Thereafter, the mi t re is complete. For conversioninto the copper comstirred at room temperature overnight. For 0011'.

plex, the whole is heated to 90, a solution of 50 V n into the coppercomplex, the dyestufi parts of crystallized copper sulfate in 300 partsSolution is then heatedto 90, a solutionv of 50 of water is added, andstirring continued at 90- P ts of crystallized copper sulfate in 300parts 95 until the methoxy group is split, with iormaof water added, andstirring continued at -95 ll 12 for hours until the methoxy groups aresplit. disulfonic acid with 1,4-dimethoxy-2-aminoben- The resultanttetrakisazo dyestufi of the formula zene, are dissolved under neutralconditions in O (Pu-O n l HQSS N=N N==N N=t':

I ufioocm 11055 I)- (II) (III) 4 (IV). is then worked up after'themanner described in "500 parts of water, '7 parts of sodium nitrite thepreceding examples and is dried at 90. added, and the whole adjustedwith 50 parts of The'new dye stuff dyes cotton and regeneratedhydrochloric acid of 30% strength at 15 so that cellulose in gray shadesof outstanding fastness it is acid to Congo. The resultant diazoniumproperties. I compound is run into a solution of 45 parts of Dyestuffsof similar properties are obtained the monoazo dyestufi used as couplingcompowhen, while otherwise preceding as described in nent in Example 1'in 400 parts of water, 1,000 the present example, the initial componentcorparts of pyridine and parts of concentrated responding to (I) isreplaced by an equivalent aqueous ammonia. The coppering and isolationquantity of 2-aminonaphthalene1-su1f0nic acid, of the resultanttetrakisazo dyestuff is carried 2-aminonaphthalene-6-sulfonic acid,Z-aminoout asin Example 1.

naphthalene-S-sulfonic acid, Z-aminonaphtha- 25 The new dyestufi of theformula 7' '7 ion, o-ou o' c =o (I) (III) I (IV) lene-8-su1fonic acid,l-aminonaphthalene-3-suldyes cotton and regenerated cellulose in grayfonic acid, 1-aminonaphthalene-7-sulfonic acid, shades of very goodfastness to light and to 1-aminonaphthalene-fi-sulfonic acid,l-aminowashing. 7

naphthalene-5-sulfonic acid, 1-aminobenzene-2- 40 Dyestuffs with similarproperties are obtained sulfonic acid, 1-aminobenzene-3-sulfonic acid:when, while otherwise proceeding as described in 1-amin0beI1Ze B -Su 0acid, this example, the azo component corresponding methylbenzene 4SulfOnic acid, 2 e i qjto I) is replaced by an equivalent quantity ofl-methylbenzene-5'sulfonic acid} 2 amino ei aminoazobenzehe-'-sulfonicacid or 4-ami nop' dimethylbenzene'3'sulfomc acid, rammazotoluol-4'-sulfonic acid, or when in the abovemethoxybenzene'4'su1fn1c acid amlde, combinations the componentscorresponding to 1-carboxybenzene--sulfomc acid, Zl-amxno-l- (In) and(IV) are severally replaced by one of carboxybfmzene'5'sufi-omc a the(III) and (IV) compounds set forth in Examacetylammobenzene-2-su1fon1cacid, l-ammo-Z- PIE chlorobenzene-i-sulfonic acid,-aminobenzenel-carboxylic acid, .2-aminobenzene-1,5-dicar- Example 7boxylic acid, 2-aminobenze-ne-1,4-dicarboxylic 455 P offihe 2iminodisazoy stuff, Obtained acid or any of the initial components mentioned bycoupling dlazotlzed -nitlobenzenein EXamme 3 or when, Starting fr m anyone f Z-sulfonic acid with 2-hydroxybenzene-l-carthe above initialcomponents, the components boxylic acid, than reducing the nitfO lp ocorresponding to (II), (III) and (IV) are re- 5 the monoazo dyestufiwith sodium sulfide, and placed by equivalent'amo nts f the (II) nfurther diazotizing and coupling with l-methoxyand 1v componentsenumerated in Exam- 2-amino-4-methylbenzene, are diazotized after p18 1.the manner described in Example 1 and then Thus, for example, thedyestuffs of the forcoupled with 48.5 parts of the copper complex ofule, 0 the monoazo dyestuif obtained by the acid coucm ou-o OH: H

is prepared in this manner; it is characterized by pling of diazotized2-amino-5-chlorobenzene-1- properties very similar to those of theinitially carboxylic acid with 2-amino-5-hydroxynaphdescribed dyestuffof the present example. thalene-T-sulfonic acid, followed by replacementEmmple 6 of the amino group by hydroxyl and then coppering; and theresultant product then subjected 52 parts of the aminodisazo dyestuff,obtained to demethylating coppering followed by isolation by couplingdiazotized 4-aminoazobenzene-3,4'- of the final dyestuff.

and dyes cotton and regenerated cellulose in gray shades of excellentfastness properties. The fastness to washing can b further enhanced byaftercoppering on the fiber.

Similar dyestuffs, also characterized by excellent properties, areobtained when, while otherwise proceeding as aforedescribed in thisexample, the component corresponding to (I) is replaced by theequivalent amount of Z hydroxy- 1carboxybenzene-3sulfonic acid,Z-hydroxy-lmethylbenzene-3carboxylic acid,B-hydroxy-lmethylbenzenel-carboxylic acid, 2-hydroxy-3-chlorobenzene-l-carboxylic acid, 2-hydroxy naphthalene-3 carboxylic acidor l-hydroxynaphthalene-2-carboxylic acid, or when in any of the abovecombinations the components corresponding to (III) and (IV) areseverally replaced by one of the (III) and (IV) compounds enumerated inExample 1.

Example 8 81.5 parts of the aminodisazo dyestufi, obtained by couplingdiazotized I-aminonaphthalene with 1aminonaphthalene-Tsulfonic acid. andthen further diazotizing and coupling with. l-methoxy2-amino4-methylbenzene, are di-azotized in the manner described inExample 3 and then coupled at with the monoazo dyestufi used as cou-4e5- pling component in Example 2, in the presence of pyridine andammonia. The demethylating coppering and isolation of the tetrakisazodyestufi isv carried out asv described in the. preceding examples.formula Ou-O (III).

(I) (II) dyes cotton and regenerated cellulose in gray shades ofoutstanding fastness to light and to washing. Y

Dyestufis with similar properties are obtained when, while otherwiseproceeding as aforedescribed in this example, the initial componentcorresponding to (I) is replaced by the equivalent quantity of2-aminonaphthalene, aminobenzene, Z-amino-l-methylbenzene; 3 amino,l-methylbenzene, 4-amino-l -methylbenzene, l-amino- 2,5-dimethylbenzene,1 amino-2,6-dimethylben- The thus-obtained dyestuff of the any of theabove combinations the components corresponding to (II), (III) and (IV)are severally replaced by the corresponding (II), (III) and (IV)compounds enumerated in Example 1.

Example 9 1 part of the dyestuif according to Example 3 (paragraphs 1and 2) is dissolved in 3000 parts of water and, to the resultantsolution, 5 parts of Glaubers salt are added. The obtained dyebath iswarmed to 50, and 100 parts of c'otton are in troduced thereinto at thistemperature. The dyebath is then heated to 95 in the course of 15 to 20minutes and maintained at this temperature for 15 minutes. Then anadditional 5 to 15 parts of Glaubers salt are added and the dyeingcontinued at 95 for about 30 --more minutes. After the bath has thencooled to 50, the dyed material is withdrawn, rinsed thoroughly anddried. A

greenish gray dyeing is obtained which is of outstanding fastness tolight and also has good wet fastness properties.

Having thus disclosed the invention, what is claimed is 1. A dyestuficorresponding to the general formula 6 will wherein a. stands for amember selected from the group consisting of diazo component radicals ofthe benzene and naphthalene series, b stands for a member selected fromthe group consisting of middle component radicals of the benzene andnaphthalene series, R stands for a radical of the benzene series, :cstands for a member selected from the group consisting of --I-I, CI-Is,-OCH3 and NI-Lacyl', y is attached ortho-positi'on to azo--- and standsfor a member selected from;

zone or 1-.amino-3,5-dimethylbenzene, or when in being connected incomplex linking with :u and -azo--, n is a whole number and at least 1,and 3. A dyestuff corresponding to the general wherein azo' stands inpara-position to formula azo", one of the substituents --O'- and whereina stands for a member selected from --Ow is attached in position 1 ofthe naphthathe group consisting of diazo component radilene nucleus andthe other in position 6, --azo 15 cals of the benzene and naphthaleneseries, 12

being attached in position 2 of the naphthalene stands for a memberselected from the group nucleus when O-w is in position 1,andinposiconsisting of middle component radicals of the tion 5 when --Owis in position 6, and benzene and naphthalene series, R stands for aazo" being attached in position 2 of the radical of the benzene series,1: stands for a memnaphthalene nucleus when O- is in position herselected from thegroup consisting of I-I, 1, and in position 5 when O isin position 6. CH3, OCHs and NHacyl, y is attached in 2. A dyestuffcorresponding to the general ortho-position to --azo and stands for asubformula stituent selected from the group consisting of wherein astands for a member selected from OH, OCHZ; and COOH, n is a wholenumthe group consisting of diazo component radicals ber and at least 1,and wherein azostands of the benzene and naphthalene series, b stands inpara-position to -azo".

for a member selected from the group consisting 4. A dyestuffcorresponding to the general of middle component radicals of the benzeneand formula all naphthalene series, It stands for a radical of thewherein a stands for a member selected from the benzene series, :vstands for a member selected group consisting of diazo componentradicals of f o the roup consis of H, CH3. OCHK the benzene andnaphthalene series, 1) stands for and is attached in ortho'posmon amember selected from the group consisting of t the respective azo-groupz-R stands for 5 middle component radicals of the benzene and ig i 223from the group conslstmg of naphthalene series, R stands for a radicalof the benzene series, .7: stands for a member selected from the groupconsisting of H, CH3, OCH; and NHacyl, y is attached in ortho positionto --azoand stands for a substituent selected from the group consistingof OI-I, OCI-Is and n being a whole number and at least 1, and whereinazo'- stands in para-position to azo"-, one of the O atoms is attachedin position 1 of the naphthalene nucleus and the otherinposi- 400E is fnumkfer and at E tion 6, and one of the --azogroups is attached andWherem Stands 1n -pos tion to in position 2 of the naphthalene nucleusand the I other in position 5. 5. The dyestufi of the formula coon cu-ol en, H038 O-Qu0(|)=0 1 0a N hP-OSKMH 18 6. The dyestuff of the formula0 m-o H0=s- N=N-ON=NGN= $11; OH; 11038 0Ou0-C=O I 03H N I'\1'-N02 7. Thedyestufi of the formula,

SOaH o--cu0 9. The dyestufl of the formula,

HANS ISCHER. ERNST ISE'LIN.

WALTER WEHRLI.

No references cited.

5. THE DYESTUFF OF THE FORMULA